Manufacture of acetoxypivalic acid by the oxidation of acetoxypivaldehyde



2,820,055 MANUFACTURE OF ACETOXYPIVALIC ACID BY THE OXIDATION OFACETOXYPIVALDEHYDE John R. Caldwell and James C. Martin, Kingsport,Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey No Drawing. Application January 27, 1955Serial No. 484,553 3 Claims. (Cl. 260-491) This invention concerns themanufacture of acetoxypivalic acid from acetoxypivaldehyde by oxidationwith nitrogen dioxide.

Acetoxypivalic acid is known in the prior art. In the preparationdescribed by Wessely in Monatshefte Fur Chemie, vol. 22, page 66 (1901),hydroxypivaldehyde is treated with potassium hydroxide to give the acidin a maximum yield of only 50% because one-half of the aldehyde isconverted to the glycol. Blaise and Marcilly, in the Bulletin SocieteChimiqne de Paris, vol. 31, pages 110-130 (1904), formed acetoxypivalicacid by condensing brominated long-chain ethers with trioxy methylene inthe presence of zinc and decomposing the resulting organo metalliccomposition with water.

An object of this invention intermediate products.

The objects of the invention are accomplished by heatingacetoxypivaldehyde with nitrogen dioxide and distilling to obtainacetoxypivalic acid.

subsequently distilled.

Our process is an improvement over the previously known methods formaking hydroxypivalic acid because hydroxypivaldehyde of acetoxypivalicacid without resorting to expensive start- It is particularly valuablefor the prduction of esters of hydroxypivalic acid.

In general, the acetoxypivaldehyde is dissolved in a suitable solvent,usually carbon tetrachloride, nitrogen dioxide is added at about 60 anesterification catalyst such as sulfuric acid or p-toluene sulfonicacid.

CHaC O O CHg+-COOH NO CH3 (3H3 HOCHzC-C'OOR CHiCOOR where R===aikylhaving 1 to carbon atoms.

2,820,055 Patented Jan. 14, less Suitable solvents include thosev thatare, unaffected by the reactants and which will also dissolve bothreactants. Examples are carbon tetrachloride, tetrachloroethane, etc.

The preferred-minimum reaction temperature is C. Below that temperaturethe oxidation proceeds rather slowly.

The following examples serve to illustrate but do not limit theinvention.

Example 1 A solution of 72 g. of acetoxypivaldehyde (0.5 mole) in 300ml. of carbon tetrachloride was heated to C.

pivalic acid with a B. P. of -112" distillatev solidified on standing.

C. at 2.5 mm. The It had the following analysis:

Neutralization equivalent (theoretical) Neutralization equivalent(found) a sodium carbonate-water slurry. After filtering, the solutionwas distilled and yielded 56.5 g. of material with a C. at 1.3 mm. Theyield of butyl hydroxypivalate was 65 W It had the following analysis:

Saponification equivalent (theoretical) 174 Saponification equivalent(found) 174 Acetoxypivaldehyde can be prepared from hydroxypivaldehydeby the method shown by Hagemeyer and to hydroxypivalic acid is readilyaccomplished by classic procedures using mineral acid catalysts.

l. A process for obtaining acetoxypivalic acid from oxide while themixture is maintained at a temperature of 2,425,029 Cass Aug. 5, 1947from 5070 C. and refluxing the mixture from 2-3 hours. 2,437,410 'Tuercket a1. Mar. 9, 1948 m f w 2,459,677 Ballard et a1. Ian. 18, 1949 azizzzims 5 EEEEE EEEEEEEEEE E Bi1st',B (13121, :30. on. 17, 1939 m an 9 pas 3E 2,176,201 Brooks 2,298,387 E Kenyon et-al. Oct. 13, 19,42

1. A PROCESS FOR OBTAINING ACETOXYPIVALIC ACID FROM ACETOXYPIVALDEHYDECOMPRISING DISSOLVING THE ACETOXYPIVALDEHYDE IN A SOLVENT SELECTED FROMTHE CLASS CONSISTING OF CARBON TETRACHLORIDE, 1,2-DICHLOROETHANE,TRICHLOROETHANE AND TETRACHLOROETHANE, ADDING NITROGEN DIOXIDE, ANDREFLUXING THE MIXTURE FROM 2-3 HOURS.